Deposition of ultra-thin inorganic oxide coatings on packaging

ABSTRACT

An apparatus and method for depositing an ultra-thin inorganic coating on to a packaging film substrate is disclosed. Flame pretreatment enhances the quality of the inorganic coating. Multiple coating layers may be deposited onto the substrate by passing the substrate over various one or more flame head configurations in either a stand-alone or in-line manufacturing environment.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of provisional U.S. Application No.61/663,555 entitled “Deposition of Ultra-Thin Inorganic Oxide Coatingson Packaging” filed Jun. 23, 2012.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to an elemental layer on a packagingsubstrate and the method and apparatus for applying the elemental layer.More specifically, the invention disclosed herein pertains to anultra-thin inorganic metal oxide layer that serves as an oxygen andwater vapor barrier layer and/or to serve as an interface for futurefunctionalization when applied to a packaging substrate. This layer canbe formed during the manufacture of the packaging substrate or in laterprocessing stages by use of known chemical vapor deposition apparatusand methods in a commercial packaging substrate manufacturing context.

2. Description of Related Art

Multi-layered packaging substrates made from petroleum-based products,polymers, copolymers, bio-polymers and/or paper structures are oftenused where there is a need for advantageous barrier, sealant, andgraphics-capability properties. Barrier properties in one or more layerscomprising the packaging substrate are important in order to protect theproduct inside the package from light, oxygen and/or moisture. Such aneed exists, for example, for the protection of foodstuffs that may runthe risk of flavor loss, staling, or spoilage if sufficient barrierproperties are not present to prevent transmission of light, oxygen, ormoisture into or out of the package. A graphics capability may also berequired so as to enable a consumer to quickly identify the product thathe or she is seeking to purchase, which also allows food productmanufacturers a way to label information such as the nutritional contentof the packaged food, and present pricing information, such as barcodes, to be placed on the product.

In the packaged food industry, protecting food from the effects ofmoisture and oxygen is important for many reasons, including health,safety, and consumer acceptability (i.e., preserving product freshnessand taste). Conventional methods to protect food contents incorporatespecialized coatings or layers within or on a surface of the packagingsubstrate, which function as an impervious barrier to prevent themigration of light, water, water vapor, fluids and foreign matter. Thesecoatings may consist of coextruded polymers (e.g., ethyl vinyl alcohol,polyvinyl alcohol, polyimides, polyamides (i.e. nylons and polyvinylacetate) and/or a thin layer of metal or metal oxide, depending on thelevel of barrier performance required to preserve the quality of theproduct stored within the package volume.

Coatings produced by chemical vapor deposition are known to providecertain barrier characteristics to the coated substrate. For example, anorganic coating such as amorphous carbon can inhibit the transmission ofelements including water, oxygen and carbon dioxide. Accordingly, carboncoatings have been applied to substrates, for example, polymeric films,to improve the barrier characteristics exhibited by the substrate.Another example of coatings applied to substrates to improve barrieradhesion performance includes coatings comprised of inorganic materialssuch as inorganic metal oxides. Ethyl vinyl alcohol and other polymerskin layers are widely used to prime or improve the wettability of filmsubstrates for the application of a barrier layer also referred toherein as “metallization primer”. Aluminum metal, aluminum oxide, andsilicon oxide are widely used for the application of barrier layer(s)directly to the substrates also referred to herein as “metallization”.

The inorganic coatings described above may be deposited onto substratesthrough various techniques as known in the art. Such techniques includephysical vapor deposition (PVD) or chemical vapor deposition (CVD)processes. Examples of PVD include ion beam sputtering and thermalevaporation. Examples of CVD include glow discharge, combustion chemicalvapor deposition (CCVD) and plasma enhanced chemical vapor deposition(PECVD) by generation of flame plasma or in strong electric fields.

The most commonly known and utilized method for depositing barrierlayers on packaging substrates for metallization requires the use of avacuum chamber to provide the vacuum environment for the deposition ofinorganic atoms/ions on to the film substrate surface. This knowntechnique, as used in the food packaging industry, consists ofprocessing packaging substrate rolls that are from less than one tothree meters wide and 500 to 150,000 meters in length running atindustry speeds of 60-600 meters/min and higher in a vacuummetallization chamber. This equipment is highly specialized, requires agreat deal of electrical power and requires large capital expense.Current vacuum chamber processes for metalizing films is inefficient inmany respects due to the high operational costs and limited productioncapacity associated with the use of such equipment. Moreover, higherquality film substrates, requiring additional capital expenditure, musttypically be used to achieve the desired barrier properties.

Combustion chemical vapor deposition (CCVD) and plasma enhanced chemicalvapor deposition (PECVD) apparatus and methods are known in the art, asdisclosed in U.S. Pat. Nos. 5,997,996 and 7,351,449, the disclosures ofwhich are hereby incorporated by reference. Typically, a combustionflame or plasma field provides the environment required for thedeposition of the desired coating (via the vapors and gases generated bythe combustion or plasma) onto the substrate. The elemental precursors(e.g. organometallics) may be vaporous or dissolved in a solvent thatmay also act as a combustible fuel. The deposition of organic andinorganic oxides may then be carried out under standard and/or openatmospheric pressures and temperatures without the need of a vacuumchamber, furnace and/or pressure chamber.

As described above, the application of barrier to food packaging isrequired to protect food and food products from the effects of moistureand oxygen. It is well known in the art that metalizing apetroleum-based polyolefin such as OPP or PET reduces the moisture vaporand oxygen transmission through specialty film by approximately threeorders of magnitude. Conventional technology employs an inorganic layerof metal or ceramic on a specialized polymer film. The inorganic layermay be aluminum, silicon, zinc, or other desired element in a metal oroxide form. However, the surface of the substrate onto which the barrierlayer will be applied is typically primed to increase its surface energyso as to be receptive to the metal barrier to be deposited thereonand/or to “smooth” the surface to be metalized so as to reduce thesurface gauge variation or surface roughness of the film to bemetalized. The term “wettability” is defined herein to include surfaceenergy, metal adhesion bond strength, and any other associatedcharacteristic that would increase the receptiveness of the film layersurface for deposition of an inorganic ultra-thin as disclosed herein.

For example, the utilization of aluminum metal as a barrier layer on lowenergy plastics, such as biaxially oriented polypropylene (BOPP) film,requires a metallization primer to reduce the gauge variation of thefilm substrate surface and/or to improve the adhesion or bond betweenthe metal and film substrate. Various chemical methods are employed toprime the substrate surface layer for improving the substrate surfaceand/or bonding of the metal barrier layer to the film substrate. Withpolymer film substrates, one method to prime the substrate formetallization is to co-extrude a specialized polymer as a skin layer onthe substrate film. These skin layers may comprise ethyl vinyl alcohol(EVOH), polyvinyl alcohol (PVOH), and polyvinyl acetate (PVA), ethylvinyl acetate (EVA), polyethylene terephthalate glycol (PETG), amorphouspolyethylene terephthalate (aPET), among other polymers used in theindustry. Unfortunately, these materials are quite expensive and addadditional cost to the manufacture of metallization ready films. Plasticfilm cores, such as oriented polypropylene (OPP), polystyrene (PS), andpolyethylene terephthalate (PET) are typically treated with coronadischarge or flame treatment. However, these treatments tend to createundesired, adverse impacts on film substrate characteristics such as theformation of pin holes, chemical degradation of the surface throughcross linking or intra-molecular chain scission that can adverselyaffect downstream metallization and heat sealing processes.

As such, there exists a need for an improved apparatus and method fordepositing an ultra-thin inorganic oxide layer onto a packagingsubstrate to prime a substrate for metallization. Likewise, a needexists in the art for an improved apparatus and method for depositingmultiple ultra-thin layers of an inorganic oxide layer on to a packagingsubstrate to enhance the barrier properties of a packaging substrate,which is less expensive and more energy efficient than traditionmetallization while achieving and maintaining high quality barriercharacteristics.

SUMMARY OF THE INVENTION

The inventive embodiments disclosed herein include a packaging substratewith an ultra-thin barrier layer and an apparatus and method forapplying an ultra-thin inorganic metal oxide barrier layer to a filmsubstrate. In one embodiment, the apparatus and method disclosed hereinuse the direct combustion of liquids, gases and/or vapors that containthe chemical precursors or reagents capable of producing inorganicoxides which are deposited on to the surface of a film substrate at openatmosphere. Chemical precursors, for example tetraethyl orthosilicate,tetramethyl disiloxane, silicon tetrachloride, silane,trimethylaluminium, triethylaluminium,methylaluminiumdichlorid-diethyletherate,trimethylaluminium-diethyletherate,ethylaluminiumdichlorid-diethyletherate, diethylaluminium-dimethylamide,aluminum trichloride, and other aluminum halides may be sprayed oratomized in an oxidant and combusted resulting in a vapor and/or gasthat is directed on to the surface of the substrate via one or moreflame heads for forming the desired coating or multiple coatingsthereon. Multiple coating layers may be deposited onto the substrate bypassing the substrate through the system in either a stand-alone orin-line manufacturing environment, or by passing the substrate overvarious one or more flame head configurations in either a stand-alone orin-line manufacturing environment as disclosed herein.

One embodiment of the present invention comprises a packaging substratesurface with an inorganic metal oxide layer of less than 50 nm thicknessthat is constructed by depositing multiple ultra-thin layers ofinorganic metal oxide on to a surface of the packaging substrate. Invarious embodiments, a preferred process that can accomplish depositionof an inorganic oxide layer onto the packaging substrate surface is CCVDor PECVD in an open atmosphere utilizing novel flame head assemblydesigns and orientations to provide and adjust as for various precursorconcentrations and coating thicknesses that are deposited on to the filmsubstrate.

In one embodiment of the invention, a method of coating a film substratewith at least one inorganic oxide layers comprises pretreating saidsubstrate by passing said substrate through at least one flame treatmentflame head assembly supplied with no inorganic oxide precursor, andafter said pretreating step, depositing one or more inorganic oxidelayers on said substrate by passing said substrate through one or moredeposition flame heads on at least one deposition flame head assemblysupplied with at least one inorganic oxide precursor, wherein saidpretreating and depositing steps occur at open atmosphere.

In another embodiment, the at least one inorganic oxide precursorcomprises at least one of tetraethyl orthosilicate, tetramethyldisiloxane, silicon tetrachloride, silane, trimethylaluminium,triethylaluminium, methylaluminiumdichlorid-diethyletherate,trimethylaluminium-diethyletherate,ethylaluminiumdichlorid-diethyletherate, diethylaluminium-dimethylamide,aluminum trichloride, and aluminum halides.

In one embodiment, the pretreating step comprising passing saidsubstrate over a portion of at least one chill roll. In anotherembodiment, the pretreating step comprises passing said substrate over aportion of multiple chill rolls. The chill roll can comprise atemperature of 40° C. to 80° C.

In one embodiment, the depositing step comprises depositing multipleinorganic oxide layers on said substrate by passing said substratethrough two or more deposition flame heads in series. In anotherembodiment, the pretreating and depositing steps occur as said filmsubstrate is unwound from one roll and wound onto a second roll. Thepretreating and depositing steps may occur in-line during manufacturingof said film substrate.

In one embodiment, the film substrate is cooled during said pretreatingstep by spraying cooling fluid on said film substrate.

In one embodiment of the invention, a system for coating a packagingfilm substrate with an inorganic oxide layer comprises at least oneflame treatment flame head assembly supplied with no inorganic oxideprecursor, one or more deposition flame heads supplied with at least oneinorganic oxide precursor placed in series on at least one depositionflame head assembly, wherein said substrate passes through said flametreatment flame head assembly before said substrate passes through saiddeposition flame head assembly, and wherein said at least one flametreatment flame head assembly and said one or more deposition flameheads are at open atmosphere.

In another embodiment, the at least one flame treatment flame headassembly or said at least one deposition flame head assembly comprisesmultiple flame head assemblies oriented in parallel rows perpendicularto a substrate movement direction.

In one embodiment, the at least one flame treatment flame head assemblyor said at least one deposition flame head assembly comprises a squareor rectangular shaped flame head assembly. In another embodiment, the atleast one flame treatment flame head assembly or said at least onedeposition flame head assembly comprises multiple flame heads assembliesoriented in rows parallel to a substrate movement direction. In stillanother embodiment, the at least one flame treatment flame head assemblyor said at least one deposition flame head assembly comprises a curvedflame head assembly.

In one embodiment, the at least one flame treatment flame head assemblyor said at least one deposition flame head assembly is oriented at anangle relative to a surface of said substrate. In another embodiment,the substrate passes through said flame head assemblies as it passesover a portion of said at least one chill roll.

In one embodiment, the inorganic precursors are fed into a flame fuelline of said deposition flame heads prior to being mixed with air froman air line and combusted at said flame heads, into an air line of saiddeposition flame heads prior to being mixed with fuel from a fuel lineand combusted at said flame heads, into an air line and a fuel line ofsaid deposition flame heads prior to being mixed and combusted at saidflame heads, or mixed with an air/fuel mixture prior to being fed tosaid deposition flame heads. In another embodiment, the inorganicprecursors is injected into a flame produced by said deposition flameheads.

The inventive embodiments described herein may be implemented instand-alone configurations, retrofitted to existing film productionlines, or installed into an in-line film substrate manufacturing and/orprocessing system. The substrate material to be coated does not need tobe heated or treated in a furnace or reaction chamber, or placed undervacuum or non-standard atmospheric conditions to effect coatingdeposition. The heat of combustion provides the needed conditions forthe reaction of the chemical precursors. The substrate material beingcoated is likewise heated by the combustion flame, which creates and/orenhances the kinetic environment for surface reactions, wettability,diffusion, film (coating) nucleation and film (coating) growth. Thechemical precursors utilized need to be properly reactive to form thedesired coating. While inorganic metal oxides are the preferred materialfor the coating applied to the packaging substrate, other elementalcoatings and compounds, for example metals, nitrides, carbides, andcarbonates may also be used as desired.

Other aspects, embodiments and features of the invention will becomeapparent from the following detailed description of the invention whenconsidered in conjunction with the accompanying figures. Theaccompanying figures are schematic and are not intended to be drawn toscale. For purposes of clarity, not every component is labeled in everyfigure, nor is every component of each embodiment of the invention shownwhere illustration is not necessary to allow those of ordinary skill inthe art to understand the invention. All patent applications and patentsincorporated herein by reference are incorporated by reference in theirentirety. In case of conflict, the present specification, includingdefinitions, will control.

BRIEF DESCRIPTION OF THE FIGURES

The novel features believed characteristic of the invention are setforth in the appended claims. The invention itself, however, as well asa preferred mode of use, further objectives and advantages thereof, willbe best understood by reference to the following detailed description ofillustrative embodiments when read in conjunction with the accompanyingfigures, wherein:

FIG. 1 depicts a cross-section view of a typical prior art foodpackaging film substrate;

FIGS. 2A-2I depict various embodiments of the apparatus and methodemployed in the present invention disclosed herein;

FIGS. 3A-3E are depictions of the apparatus and method as integratedinto in-line packaging substrate production and manufacturing equipmentaccording to one embodiment of the invention disclosed herein;

FIG. 4 is a cross-sectional depiction of a film substrate with multiplecoating nanolayers according to one embodiment of the inventiondisclosed herein; and,

FIGS. 5A-5I are depictions of various apparatus embodiments which may beemployed in the present invention disclosed herein.

FIG. 6 is a graph showing, for a single deposition pass of silica, theamount of silica deposited as determined by signal strength viainformation collected by XPS.

FIG. 7 is a graph showing a signal strength (CPS) vs. binding energy(eV) from XPS for multiple passes; and

FIG. 8 is a graph showing the atomic percentage of silicon atoms on thefilm surface, WVTR, and OTR values plotted versus the number of silicadeposition passes.

DETAILED DESCRIPTION

FIG. 1 depicts a schematic cross-section of a typical, currently usedfood packaging multi-layer or composite film substrate 10. Film 10 isconstructed of various intermediate layers that act in concert toprovide the film 10 with the required performance characteristics. Forexample, a graphics layer 14 allows a graphic to be printed or otherwisedisposed thereon and is protected by transparent exterior base layer 12which may consist of oriented polypropylene (OPP) or polyethyleneterephthalate (PET). A glue or laminate layer 16, which is typically apolyethylene extrusion, acts to bind the exterior base layer 12 with theinner, product-side base layer 18. A metal layer may be disposed uponinner base layer 18 by means of metallization known in the art. Sealantlayer 20 is disposed upon the OPP or PET interior base layer 18 toenable a hermetic seal to be formed at a temperature lower than the melttemperature of the interior base layer 18. Each layer described isformed as a roll of film that is then unwound and laminated together toform the composite film. Each film being laminated together forms thecomposite films, which are film structures composed of multiple layerswhen originally extruded or fabricated.

Alternative materials used in the construction of packaging filmsubstrates may include polyesters, polyolefin extrusions, cellulosicpolymers, acetate polymers, adhesive laminates, bio-films such aspolylactic acid (PLA) films and polyhydroxy-alkanoate (PHA) films,produced in various combinations resulting in composite, multi-layeredfilm structures. The film substrate may be formed by typicalcoextrusion, lamination, or extrusion coating techniques as known in theart. The film substrate can also be composed of polyimide, liquidcrystal, polyethylene, or other materials normally used in electronic,optic or specialty packaging or multilayer applications.

In both PECVD and CCVD processes described herein, the localizedenvironment required for coating deposition to occur is provided by theflame, plasma or other energy means. With CCVD and PECVD no furnace,auxiliary heating, or reaction chamber is necessary for the reaction tooccur. Further, both CCVD and PECVD can be carried out inopen-atmosphere conditions. The plasma or flame supplies the energyneeded for coating deposition in the forms of the kinetic energy of thespecies present and radiation. This energy creates the appropriatethermal environment to form reactive species and coincidentally heatsthe substrate, thus providing the kinetic conditions for surfacereactions, diffusion, nucleation, and growth to occur. When usingcombustible solutions, the solvent plays two primary roles. First, thesolvent conveys the coating reagents into the vicinity of the substratewhere coating deposition occurs, thereby allowing the use of low costsoluble precursors. Uniform feed rates of any reagent stoichiometry canbe produced easily by simply varying the reagents' concentrations insolution and the solution flow rate. Second, the combustion of thesolvent produces the flame required for CCVD and PECVD.

In general, the deposition processes described herein are performedunder ambient conditions in the open atmosphere to produce an inorganicfilm on a substrate. The film preferably is amorphous, but may becrystalline, depending on the reagent and deposition conditions. Thereagent, or chemically reactive compound, is dissolved or carried in asolvent, typically a liquid organic solvent, such as an alkene, alkideor alcohol. The resulting solution is sprayed from a nozzle usingoxygen-enriched air as the propellant gas and ignited. A substrate ispositioned at or near the flame's end. Flame blow-off may be preventedby use of a hot element such as a small pilot light. The reactants arecombusted in the flame and the ions or radicals generated from thecombustion are deposited on the substrate as a coating. For the presentinvention, the formation and rate of deposition of the inorganic oxidelayer(s) are important to the quality of the coating produced and theinvention disclosed herein describes in various embodiments and examplesof the equipment and processes for producing such quality coatings.

The methods and apparatus utilized to perform the inventive methodsdisclosed herein provide a less-energy intensive and more efficientmethod for the surface treatment of film substrates for a variety ofapplications. For example, priming a substrate for metallization isusually required to enhance the wettability of the substrate surface forthe reception of a metalized layer. As previously discussed, prior artmethods of priming a substrate for metallization typically require theaddition of a skin layer via coextrusion or solution coating of chemicaladditives such as EVOH and/or treatment by flame or Corona dischargeprior to metallization. The apparatus and methods herein provide a novelmethod by which the surface energy of the film substrate is raisedtypically between 1 and 10 dynes by the addition of the inorganic primernanolayer, thereby enhancing the wettability of the substrate surfaceand thus improving the adhesion between the deposited metal barriercoating and the substrate.

It is also important for the inorganic oxide layer(s) to enable futurevapor deposition of barrier, printing or adhesive layers applied to thefilm substrate to adhere well and for hot seal processes to stillfunction as desired. An integral aspect of the invention includesapplication of the inorganic oxide layer to the film substrate so as toimprove the surface wettability of the substrate surface for futureapplications.

By using different inorganic materials, additional properties can becreated to enhance the use of the film for various applications. Forexample, use of silver can provide antimicrobial/disinfectionproperties. In other embodiments, ultraviolet radiation blockinginorganics, including zinc oxides and tin oxides may be utilized to forma clear ultra-violet light and gas barrier layer. Other transparentmaterials, for example silica oxide, may be used to form and/or act asultra-thin barrier layer(s).

A key economic feature in using polymer-based products is maintaininglow cost. As a result, the inorganic materials used as nanolayercoatings are typically selected from low cost inorganic elements. Also,the health aspect of the materials used in the formation of films forpackaging is very important since the polymer films are used most oftenin consumer products including food and medical packaging. Thus, healthsafe materials, for example silica-based inorganics, may be utilized invarious embodiments. Silica is the most common oxide of the earth'scrust and soil and long-term storage in glass containers has extensiveproven history as a safe and effective storage medium with regard tohuman health requirements.

The use of current surface modifying materials in film productionrepresents a significant volume and weight fraction of the end productthus reducing its recyclability. The present invention greatly reducesthe material required to form the desired barrier thickness, resultingin a more recyclable and/or compostable product. In one an embodiment,the inorganic oxide layer is generally less than 10 nm thick and morepreferably less than 5 nm average thickness. Due to the small thicknessof such a layer, the inorganic oxide layer more readily breaks intosmaller pieces resulting in a higher grade of recyclable material. Infact, silica is often used as an enhancement additive to polymers toimprove strength and durability. One embodiment of the inventionincludes an inorganic oxide layer that alters the bulk physicalproperties of film base polymer, as compared to reprocessing of neatpolymer, by less than 1%.

For biodegradable polymers, such as PLA and PHA, a barrier layer appliedto a film substrate incorporating PLA and/or PHA or other bio-polymermay in fact detract from the desired degradability of the packagingmaterial resulting therefrom. Such a barrier layer reduces thetransmission of moisture or oxygen that can affect the degradationprocess of the film package. Multiple layers of barrier can result in apackage that does not degrade due to the core film substrate material(barrier on both sides) never being exposed to the proper environmentfor decomposition. An embodiment of the present invention includesforming an inorganic oxide coating that alone does not provide animpervious barrier, but enables subsequent printing, adhesion layers, orquality barrier layer(s) to be deposited upon the inorganic oxidecoating in an online manufacturing context or a secondary downstreamfacility. In one embodiment, the inorganic oxide layer can be depositedon both sides of the packaging substrate for a variety of contemplatedend uses.

One of the key uses of the smooth inorganic ultra-thin layer issubsequent barrier layer formation thereon. Thin film metallization oroxide barrier layers adhere to and perform better on smooth surfaceswith low defects. Polymer films readily form such surfaces duringmanufacturing, but the addition of anti-block agents as currently usedin the industry cause an increase in the film's surface roughness anddefects, with RMS generally greater than 100 nm. A key aspect of thepresent invention results in packaging substrates with surface roughnessthan 30 nm RMS, and more preferably less than 10 nm RMS, and in somecases less than 5 nm RMS.

In another embodiment, the invention disclosed herein produces theability to maintain low surface RMS values while controlling the surfacewetting properties. The surface tension can be controlled by acombination of the inorganic ultra-thin layer's surface roughness andalso the termination material on the surface. To improve the adhesion ofinorganic barrier layer materials to the substrate, it is desired that asurface of the substrate be receptive to metal or inorganic oxide ionicor covalent bonding. Inorganic oxide surfaces provide excellent bondingsites for both metal and oxide layers, along with a smooth surfacecoating. It has been discovered that surface smoothness enhances theformation of barrier layer(s) on the substrate. For barrier depositionapplications, it is preferred that the substrate surface to be coatedhas a smooth, low texture surface on both the nanometer and micrometerscale.

One key to successful application of such interface layers is to formand apply the primer and barrier layers to the substrate prior towinding or rolling of the film. Films are made by a number of processesincluding cast and blown films. These processes are typically performedat ambient atmosphere and pressure on large production lines. Theintroduction of prior art vacuum deposition equipment into such a linemakes such processes economically impractical. Thus, a method forforming films online with an inorganic ultra-thin layer at ambientpressure on low temperature polymers is a better pathway to accomplishsuch an inventive ultra-thin layer. Aspects of how to do this with aprocess such as CCVD are disclosed in U.S. Pat. No. 5,652,021 (Hunt etal.) and U.S. Pat. No. 5,863,604 (Hunt et al.), the disclosures of whichare incorporated herein by reference.

In order to form an effective barrier layer in subsequent processingoperations, it is important for the film substrate surface to be smooth.Thin film barrier requires a smooth substrate surface without featuresthat can shadow or inhibit the thin film material from being depositedonto the vast majority of the entire surface. It is preferred that atleast 90% of the substrate surface be coated and even more preferredthat over 99% be accessible to vapor deposition material without surfaceroughness that can cause shadowing or thin film defects. It is alsoimportant that the inorganic primer layer is very smooth so that it willnot impact the dense uniform continuous growth of additional inorganicoxide layer(s) deposited thereon to build an effective thin film barrierlayer. Columnar growth on the inorganic primer layer will have anegative impact on the subsequent growth of a vacuum deposited or otherthin film barrier layer applied thereto. The end effect is that asubsequent barrier layer can be grown to yield a Oxygen TransmissionRate (OTR) of less than 10 cc/m²/day @ 23° C. and 0% RH and a WaterVapor Transmission Rate (WVTR) of less than 2 g/m²/day @ 38° C. and 90%RH, more preferably OTR<2 cc/m²/day @ 23° C. and 0% RH and WVTR<1g/m²/day @ 38° C. and 90% RH, and even more preferably OTR<1 cc/m²/day @23° C. and 0% RH and WVTR<0.2 g/m²/day @ 38° C. and 90% RH on substrateswhere an inorganic primer layer is deposited prior to the barrier layer.In one embodiment, the primer and/or barrier layer is transparent tolight in the visible spectrum. In alternative embodiments, thesubsequent primer and/or barrier layers may be translucent or opaque asappropriate for effective utilization of the coated substrate forflexible packaging or other contemplated end uses.

The current invention also has minimal environmental impact and yields asafer packaging material as a result of the reduction in the number oforganic chemicals blended into the polymer film substrate. Suchadditives can cause health concerns or can reduce the quality ofrecyclable material. Silica, alumina, and the other elements of thepresent invention are common in the earth's crust, are often used asfood additives, and have been used safely in glass containers for manyyears. As a result, the invention disclosed herein utilizes plentifuland non-toxic, safe inorganic materials with essentially no detrimentalenvironmental impact.

Multilayer packaging substrates may be produced with excellent bondingcharacteristics provided by application of one or more ultra-thininorganic oxide layers as described herein. In various embodiments,moisture, oxygen and light can pass through the inorganic oxide layer(s)so that compostable polymer film structures can still be decomposedunder typical environmental conditions. The inorganic oxide coating withproper selection of metalloid or metal element, such as silicon oraluminum, creates a thin coating that will not inhibit composting of thefilm substrate and has absolute minimal impact on the environment.

In one embodiment disclosed herein, a PECVD or CCVD apparatus is used todeposit one or more ultra-thin layers of silica oxide (SiO_(x)) and/orother inorganic oxides on the surface of the substrate in an openatmosphere environment thereby increasing the substrate surface energyand improving the adhesion of the metal barrier layer with thesubstrate, effectively “priming” the substrate for metallization. In oneembodiment disclosed herein, a PECVD or CCVD apparatus is integrated“in-line” with a packaging substrate manufacturing line there forpriming the substrate for metallization before being wound into a roll.

Various embodiments of the present invention disclosed herein alsocomprise apparatus and methods for applying a barrier layer to thesurface of a packaging substrate at open atmosphere. The apparatus andmethod disclosed herein provide for the direct combustion of liquidsand/or vapors that contain the chemical precursors or reagents to bedeposited on to the surface of a substrate material at open atmosphere.Metal oxides, for example, aluminum oxides, are formed from thecombustion of materials, such as organo-aluminum compounds with anoxidant, and combusted resulting in a vapor and/or gas at openatmosphere that is directed on to the surface of the substrate andresulting in the deposition of the desired coating thereon.

In accordance with an embodiment of the invention disclosed herein, FIG.2A depicts a flame CCVD apparatus that is supplied with combustiblechemical precursors for the deposition of an inorganic oxide coating onto a substrate. The system operates to break the chemical precursorsinto micron and sub-micron sized droplets in the combustion zone for theapplication of the ultra-thin coating process disclosed herein.

Turning to FIG. 2A, a general schematic of the apparatus 40 that isutilized to carry out the coating deposition process is shown. Chemicalprecursors 42 may comprise a solvent-reagent solution of flammable ornon-flammable solvents mixed with liquid, vaporous, or gaseous reagentssupplied to flame head assembly 44 or other flame-producing device. Theterm “flame head assembly” is used to refer generally to describe anyapparatus that is capable of producing a flame from a fuel feed,including flame treaters, flame burners and flame head devices asdescribed herein and which are commercially available from variousmanufacturers. Chemical precursors 42 are ignited in the presence of anoxidant 46 resulting in a flame 48. As the chemical precursors 42solution or mixture burn, the reagent reacts to form an inorganic vaporand leaves the flame 48 along with other hot gases 50 and combustionproducts. The substrate 52 to be coated is located proximal to flame 48within the region of gases 50. In one embodiment, substrate 52 isoriented tangentially to the flame 48, or as shown in FIG. 2B substrate52 is oriented obliquely to the flame 48, or at any angle facing theflame end 54 of flame 48 such that the hot gases 50 containing thereagent vapor will contact the substrate surface 56 to be coated. Invarious embodiments, substrate 52 may consist of a film or compositefilm comprising oriented polypropylene (OPP), polyethylene (PE),polylactic acid (PLA), polyhydroxy-alkanoate (PHA), polyethyleneterephthalate (PETP), other polyesters, or other known polymer,biopolymer, paper or other cellulosic substrates, alone or incombination, as known in the art.

FIG. 2B is similar to the apparatus 40 shown in FIG. 2A, but isconfigured for a non-turbulent flame methodology, suitable for chemicalprecursors comprising gaseous precursors 42 and non-flammable carriersolutions 46. Flame 48 produced by the flame head assembly 44 atypically has the flame characteristics of an inner flame 48 a definingthe reducing region where the majority of oxidizing gas supplied withthe reagent burns and an outer flame 48 b defining the oxidizing regionwhere the excess fuel oxidizes with any oxidizing gas in the atmosphere.In this example embodiment, the substrate is positioned at an obliqueangle proximate to the flame end 54 of the flame 48 such that the hotgases and/or vapors 50 containing the reagent vapor will contact thesubstrate surface 56 of substrate 52.

Referring back to FIG. 2A, the precursor mixture 46 is supplied to theflame head assembly 44. Oxidant 46 is also supplied to the flame headassembly 44 in some fashion, via a separate feed, or is present in theprocess atmosphere, or the oxidant may be supplied by a separate feed tothe process atmosphere or flame ignition point, or the oxidant may bepresent in the reagent mixture. In the depicted embodiment, the chemicalprecursor solution 42 is ignited in the presence of oxidant 46 andcombust in flame 48 resulting in the generation of heat, gases and/orvapors 50. The generation of heat causes any liquid reagent solutionspresent to vaporize and increase the temperature of the substrate 52 soas to result in improved surface diffusion of the coating resulting in amore uniform coating deposited onto the substrate surface 56.

In performing CCVD or PECVD coating deposition on film substrates,certain deposition conditions are preferred. First, the substrate needsto be located in a zone such that it is heated by the flame's radiantenergy and the hot gases produced by the flame sufficiently to allowsurface diffusion. This temperature zone is present from about themiddle of the flame to some distance beyond the flame's end. Thetemperature of the flame can be controlled to some extent by varying theoxidant-to-fuel ratio as well as by adding non-reactive gases to thefeed gas or non-combustible miscible liquids to the feed solution.Secondly, the metal-based precursors need to be vaporized and chemicallychanged into the desired state. For oxides, this will occur in the flameif sufficient oxygen is present. The high temperatures, radiant energy(infrared, ultraviolet and other radiant energy), and plasma of theflame also aid in the reactivity of precursors. Finally, for singlecrystal films, the material being deposited should be in the vaporphase, with little or no stable particle deposition. Particle formationcan be suppressed by maintaining a low concentration of solutes, and byminimizing the distance, and therefore time, between locations where thereagents react and where the substrate is positioned. Combining thesedifferent factors predicts the best deposition zone to be located inproximity of the flame's tip. If a solution is sprayed, droplets canstrike a substrate located too far into the flame proximity, possiblyresulting in some spray pyrolysis characteristics in the resulting film.In fact, in some configurations, with large droplets or with somereactants, it may be impossible to not have some spray pyrolysis occur.

In various embodiments of the invention disclosed herein, a plasma torchmay also be used in a manner similar to a flame apparatus to achievesimilar results. Chemical precursors are sprayed through a plasma torchand deposited on to the substrate. The reagents and other matter fedthrough the plasma torch are heated and, in turn, heat the substratesurface, much in the same manner by the flame embodiment describedherein. In plasma enhanced chemical vapor deposition, lower plasmatemperatures may be used as compared to conventional plasma spraying, aslower heat is required to cause the chemical precursors to react. As aresult, the chemical precursor reactions occur at lower temperaturesthereby allowing substrates with low melt points to take advantage ofPECVD. The deposition of the coating on to the substrate results fromdirecting of the plasma gas vapor containing the charged ions in thedirection of the substrate. For example, a chemical precursor gasmixture or solution is fed into a plasma flame resulting in theformation of a chemical vapor. The chemical precursor solution maycomprise inorganic metal oxides such as aluminum oxide or silicon oxide.Once oxidized, the resulting ions in substantially vapor form aredirected onto the surface of the substrate resulting in the formation ofa solid coating formed on the surface of the substrate and which aretypically formed with thicknesses in the 1 to 50 nanometer range.

In general, as long as a flame is produced, CCVD or PECVD can occurindependently of the flame temperature or substrate surface temperature.The flame temperature is dependent on the type and quantity of reagent,solvent, fuel and oxidant used, and the substrate shape and material,and can be determined by one skilled in the art when presented with theparticular reagent, solvent, fuel, oxidant and other components andconditions for deposition. The preferred flame temperature near thedeposition surface on a moving web line is between about 800° C. and1300° C. As flames may exist over a wide pressure range, CCVD can beaccomplished at a pressure from about 10 torr to about thousands oftorr, but it is preferred to be at ambient pressure to ease its use onthe polymer film processing line. Likewise, if plasma is formed fordepositing the coating, the temperature of the plasma can range fromabout 400° C. to about 1200° C. The temperature of the substrate duringthe CCVD process also can vary depending on the type of coating desired,the substrate material, and the flame characteristics. Generally, asubstrate surface temperature of between about 40° C. and 80° C. ispreferred for temperature sensitive polymer films.

The deposition rate of the coating onto the substrate can vary widelydepending on, among other factors, the coating quality, the coatingthickness, the reagent, the substrate material and the flamecharacteristics. For example, increasing the exposure period of the filmsubstrate to the vapor stream emanating from a flame head can result inthicker coatings deposited on the film substrate, assuming a relativelyconstant precursor feed flow rate to the flame generated at the flamenozzle. Less porous coatings are possible assuming a relatively lowerfeed flow rate to the flame generated at the flame nozzle or more porouscoatings assuming a relatively greater feed flow rate to the flamegenerated at the flame nozzle. Likewise, if a higher quality coating isdesired, a longer exposure time at a lower precursor feed flow rate maybe necessary, while a gross or textured coating can be producedrelatively quickly using a greater precursor feed flow rate. One skilledin the art can determine the precursor feed flow rates and exposureperiods necessary to produce a desired coating on the film substrate.Typical deposition rates on product made using the apparatus and methodsdisclosed herein range from about 10 nm/min to about 1000 nm/min withthe film surface being normally exposed to the flame for 0.1 to 10seconds. As discussed above, the chemical precursor solution in oneembodiment is a liquid reagent dissolved in a liquid solvent. However,solid, liquid, vaporous and gaseous reagents can be used, with a liquidor gaseous solvent, as long as the chemical precursor feed to the flameis typically liquid or gaseous in nature.

Referring to FIG. 2C, one embodiment of the invention disclosed hereinis shown wherein a flame redirect source is shown. The flame redirecttechnique employs an air knife 49 situated at an angle to the flame 48to redirect the gases and/or vapors 50 from the process. The air knife49 directs an air stream into the vapor stream 50 coming from the flame48. This effectively redirects the vapor stream 50 in the desireddirection of the substrate surface 56 while at the same time deflectingthe heat stream associated with flame 48 from overheating or melting thesubstrate 52 being coated with the vapor 50. This method results in thedissipation of heat directed on to the substrate 52 from the flame 48heat stream thereby resulting in the deposition of desired coating on tothe substrate surface 56 at lower temperatures.

The redirect flame embodiment also acts to disperse the gas and/or vaporstream 50 emanating from the flame 48 resulting in a wider depositionstream 50 being directed on to the substrate surface 56 and enlargingthe coating area of same. In an alternative embodiment, anelectromagnetic or “electro-redirect” method may be employed to redirectthe deposition of ions and/or particles emanating from a flame and/orplasma source on to the substrate surface. In this embodiment, the flameand/or plasma source initially directs the ion and/or particle streamand any associated heat in a substantially parallel direction to thefilm substrate to be coated. A field with an electrical potential isgenerated by means as is known in the art that passes through a portionof the film substrate resulting in the redirection and/or accelerationof the ion and/or particle stream emanating from the flame or plasmasource on to the film surface. The chemical bonds within the polymermolecules are more readily broken which results in the rapid formationof free radicals. This results in the deposition of the desiredultra-thin coating on to the film surface without the associated heatbeing transferred to the film surface thereby preventing potentialmelting of the film substrate during the deposition process.

With reference to FIG. 2D, one embodiment of the invention disclosedherein is shown with multi-flame head system 60. In this embodiment,system 60 includes a flame head assembly 62 comprising a pipe withspaced holes or nozzles for emitting flames and referred to as flameheads 64 integrated therewith. In various embodiments, such flame headassembly 62 may comprise commercially available flame burner headsmanufactured by Flynn Burner Corporation of New Rochelle, N.Y. Chemicalprecursors 61, which may also include an oxidant, are fed into flamehead assembly 62 and when ignited result in lit flames emanating fromflame heads 64 resulting in the generation of hot gases and/or vapors66. The substrate 52 to be coated is located proximal to flame heads 64within the region of hot gases and/or vapors 66, such that hot gasesand/or vapors 66 containing the reagent vapor will contact the substratesurface 56 resulting in a coating deposited thereon. The multi-headflame head deposition system 60 improves the continuity and thickness ofcoating deposition across the substrate surface 56 as the hot gas and/orvapor region 66 is expanded by the use of multiple flame sources. System60 depicted in FIG. 2D is shown with flame head assembly 62 aligned withmultiple flame heads positioned in a planar and/or linear orientation.However, other embodiments are contemplated wherein one or more flamehead assemblies may be designed in various two-dimensional andthree-dimensional geometries such as square, rhomboid, cylindricalshapes which may be fashioned and positioned relative to the film beingprocessed according to the necessity of the user as depicted in FIGS.2E, 2F, 2G, 2H and 2I. In these alternative contemplated embodiments,one or more precursor(s) may be fed to select flame heads in theindividual flame head assembly providing the user with the ability tovary the type, characteristics and thickness of the coating deposited onto a substrate. As can be readily seen in these figures, the shape ofthe individual flame heads and flame head assemblies and theirorientation relative to the substrate may be configured to achievedifferential types, concentrations and/or thicknesses of ultra-thincoating deposition on to the substrate by the apparatus and methodsdescribed herein.

For example, FIG. 2E discloses multiple flame head assemblies 68oriented in parallel rows perpendicular to the direction of thepackaging substrate 52 movement. By orienting the flame head assemblies68 in this fashion, multiple coatings may be deposited on the substrate52 in one pass along the indicated direction of substrate 52 travel. Inone embodiment, various concentrations, gradients of precursorconcentrations or different precursors may be fed to each individualflame head assembly 68, or to each individual flame head integrated intoeach flame head assembly 68 to vary the type of coating layers and/orconcentration of coating layers and/or thickness of coating layersdeposited on to substrate 52. In one embodiment, one or more of theflame head assemblies 68 emit a flame for purposes of priming the filmsubstrate 52 via flame treatment. After passing through the flametreatment flame head assemblies, the substrate encounters one or more ofthe latter positioned flame head assemblies 68 which may be suppliedwith a precursor or various precursors for application of an ultra-thincoating on the flame-treated substrate 52 as desired by the user.

FIG. 2F discloses a curved flame head assembly 70 that provides fordeposition of an ultra-thin inorganic oxide layer on to a substrate 52as it passes over a portion of chill roll 72 and is held in relativecontact with chill roll 72 via placement of nip rollers 74. In oneembodiment, various concentrations, gradients of precursorconcentrations or different precursors may be fed to the curved flamehead assembly 70, or to each individual flame head integrated into thecurved flame head assembly 70, to vary the type of coating layers and/orconcentration of coating layers and/or thickness of coating layersdeposited on to substrate 52.

FIG. 2G depicts a square or rectangular shaped flame head assembly 76that provides for deposition of an ultra-thin inorganic oxide layer onto substrate 52. In one embodiment, various concentrations, gradients ofprecursor concentrations or different precursors may be fed to the flamehead assembly 76, or to each individual flame head integrated into theflame head assembly 76, to vary the type of coating layers and/orconcentration of coating layers and/or thickness of coating layersdeposited on to substrate 52.

FIG. 2H discloses multiple flame heads integrated into flame headassemblies 68 oriented in parallel rows parallel to the direction of thepackaging substrate 52 travel. In one embodiment, variousconcentrations, gradients of precursor concentrations or differentprecursors may be fed to each individual flame head assembly 68, or toeach individual flame head integrated into each flame head assembly 68to vary the type of coating layers and/or concentration of coatinglayers and/or thickness of coating layers deposited on to substrate 52.

Turning to FIG. 2I, one embodiment of the invention disclosed hereindepicts a flame head assembly 78 oriented at an angle relative to thesubstrate 52 surface. In this configuration, one end of the flame headassembly 78 is closer to the substrate surface as the substrate 52 movesin the longitudinal direction parallel to the flame head assembly 78. Inone embodiment, the “lower” end of the flame head assembly 78 ispositioned at substantially 20 mm above the surface of substrate 52 andserves to precondition the substrate 52 as it provides a more intensiveheat treatment upon introduction of the substrate 52 to the proximity offlame head assembly 78 and would serve to clean off dirt, dust and othercontaminants that may be on the substrate surface. As the substrate 52moves along, the “upper” end of the flame head assembly 78 is positionedsubstantially 40 mm above the surface of substrate 52 and resulting inlower intensity heat treatment applied to the substrate 52 due to theincreasing distance between the surface of substrate 52 and the flamehead assembly 78. Therefore, various concentrations of precursor couldbe fed to select or all of the remaining flame heads in the flame headassembly 78 resulting in the differential application of inorganic oxidelayers to the surface of substrate 52 as it moves along the length ofthe flame head assembly 78. In one embodiment, the flame head assembly78 is oriented at a 2 mm distance from the substrate 52 surface at theinitial encounter between the flame/plasma with the substrate 52 surfaceand oriented at an inclined angle to produce a 4 mm distance between thesubstrate 52 and the last flame head in the flame head assembly 78 asshown. In alternative embodiments, the flame head assembly 78 may beoriented at inclined angles perpendicular or along a radial arc relativeto the direction of the substrate 52 to achieve flame pretreatment orvariegated organic oxide layer deposition on the substrate 52 asdesired.

Such configurations and shapes would increase the film surface areaexposed to the flame in a single pass of the film substrate past theburner. In turn, these geometric configurations increase the dwell timethe flame or plasma has in contact with the film substrate surfacethereby altering the coating properties imparted to the film substrate.Therefore, the embodiments depicted herein are not to be construed aslimiting to the disclosure herein.

Turning to FIG. 3A, one embodiment of a CCVD and/or PECVD coatingassembly as described herein is shown “in-line” with a roll-to-rollwinding/coating assembly 80 in a typical manufacturing context. In thedepicted embodiment, an unwinding unit 86 unwinds film 88 from roller 96as winding unit 84 winds film 88 on to winding core 94. A flame chamber82 housing a CCVD and/or PECVD coating assembly 92 as described hereinis integrated in-line with the unwinding/winding units 86 and 84. Theflame chamber 82 constitutes an unpressurized enclosure in which atleast one CCVD and/or PECVD flame head assembly 92 is housed for thesafety of the user and surrounding equipment and materials. During theunwinding/winding process, a film substrate 88 is drawn from unwindingunit 86 through various rollers and on to drum 90. After receiving acoating and exiting the flame chamber 82, film substrate 88 is woundaround winding core 94. Drum roller 90 rotates and winds and/or drawssubstrate 88 in proximity to the hot gases and/or vapors generated bythe flame head assembly 92. In the depicted embodiment, drum roller 90is positioned above flame head assembly 92 so as to maximize the surfacearea contact between the rising hot gases and/or vapors generated byflame head assembly 92 thereby resulting in efficient deposition of thecoating material carried by the hot gases and/or vapors on to substrate88. In various contemplated embodiments, drum roller 90 may comprise atemperature control roll or “chill roll” so as to impart a thermaltemperature to the substrate and a differential between the substrate 88to be coated and the heat generated by the flame head assembly 92 whichwould facilitate coating substrates with low melt points without heatdamage to the substrate according the inventive method and apparatusdisclosed herein. In the embodiment depicted in FIG. 3B, multiple flameassemblies 82 are integrated in-line to provide multiple coating layersto the substrate 88. In this configuration, multiple layers ofultra-thin inorganic coatings of variable type, concentration and/orthickness may be applied to the substrate at each flame head assembly 82station as desired and configured by the user.

With reference to FIGS. 3A and 3B and without being bound by theory, ithas been discovered that better quality deposition coatings (i.e.improved coating layer coverage uniformity over the substrate surfaceand enhanced RMS smoothness of the deposited coating layer) may beachieved by passing the substrate film multiple times through the flametreatment system or past multiple flame heads and/or flame headassemblies, with low concentrations of precursor, as opposed to a singlepass of the substrate through a flame treatment system using a highconcentration of precursor resulting in one thick deposition layer. Inone example embodiment, a stand alone roll-to-roll coater was equippedwith a single burner plasma flame treatment system. A combustibleinorganic precursor, tetraethyl orthosilicate (TEOS), was metered intothe fuel stream at a controlled rate. As the film was unwound and passedover the plasma flame, low concentration levels of silica were depositedonto the surface of the film substrate. Collected data revealed that theSiO₂ deposition quality was poor where the TEOS concentration wasgreater than 22 mg/min, SiO₂ deposition quality was rated as good wherethe TEOS concentration was less than 11 mg/min, and SiO₂ depositionquality was rated as excellent where the TEOS concentration level wasless than 2 mg/min. As the film was passed multiple times (between twoto five passes) over a plasma flame fed with low concentration TEOS,multiple layers of SiO₂ were deposited on the film substrate whichresulted in the development of a barrier layer with a thickness of 50 nmand exhibiting an OTR<10 cc/m²/day and a WVTR<0.5 g/m²/day.

The metallization primer process described herein may be conductedeither during (“in-line”) or after film manufacturing. The film surfacemanufacture in-line is commonly pristine and free of contaminantsthereby making it ideal for surface priming due to the challenges ofkeeping the film surface clean after the manufacturing process iscomplete. For example, dust, anti-block particles, or additives in thepolymer film may “bloom” to the surface of the film substrate in apost-manufacturing environment. These conditions can make it difficultto achieve a uniform primer coating during the priming process conductedafter the film has been manufactured and stored for a period of time.Blooming additives can also migrate over the inorganic nanolayer, as itis not a barrier layer in itself, thus it is desired not to have theseadditives in the film.

Turning to FIG. 3C, one embodiment of the invention disclosed herein isshown wherein a flame CCVD or PECVD unit is installed in-line with abiaxial film substrate production line 100. In the depicted embodiment,a biaxial film substrate 102 is formed by an extrusion unit 104. Thefilm substrate 102 is then passed through a cooling unit 106 and isstretched in the machine (longitudinal) direction in machine stretchingunit 108 and in the transverse direction in transverse stretching unit110. The film substrate is then passed through the flame head assembly112 wherein it is coated with the desired inorganic primer and/orbarrier coating according to the apparatus and processes describedherein. The coated film substrate is then wound into a transportableroll in winding unit 114 for further processing or distribution.

With reference to FIG. 3D, an embodiment of the invention disclosedherein is depicted wherein a flame CCVD or PECVD coating tower unit 118is installed in-line with a biaxial film substrate production line 100as similar to the production line depicted in FIG. 3C. In thisembodiment, multiple flame head assemblies 120 are placed in series witheach delivering a low concentration of inorganic precursor as thesubstrate 102 passes through the line over various chill rolls and niprolls in a single pass through the system. The flame head assemblygeometry, substrate line speed, chill roll temperature and precursortypes and concentration could be configured in various contexts toproduce the desired type, concentration and/or thickness(es) ofultra-thin inorganic coating(s) to be deposited on the particularpackaging substrate. Typical processing conditions are as follows: linespeeds from 200 to 1500 ft/min (60 m/min to 450 m/min); chill rolltemperatures of 40 to 80° C.; the flame pretreatment with burner to filmdistance of 5 mm for flame pretreatment, a fuel to air ratio of 0.90 to0.95 for the flame treatment step, a natural gas flow rate of 100liters/min for a 1 meter wide line; the deposition step with burner tofilm distances of 5 to 45 mm, a fuel to air ratio 1.0, gas flow rates of70 to 105 liters/min for a 1 meter wide line, a precursor concentrationof 0.0001 mole % to 0.01 mole % of the gas stream. The plasmatemperatures have exhibited good results at 1200° C. with a rangecovering 650° C. to 1450° C. The above conditions will produce a coatingwith a WVTR of <0.2 g/m²/day and an OTR<20 cc/m²/day.

Managing heat buildup in the substrate from exposure to PECVD or CCVDflame head is of great concern as such heat buildup will distort or meltthe substrate being coated. As described in various embodiments shownand disclosed herein, chill roll technology is used to dissipate heatbuildup in the substrate. However, the diameter of the chill roll ornumber of multiple chill rolls required to accomplish certain coatingsmay be cost or space prohibitive due to size/space limitation in themanufacturing environment. Alternatively, spray coolants may be utilizedto dissipate heat buildup in the substrate as it is treated according tothe apparatus and methods herein that are practiced in limited spaceenvironments. As depicted in FIG. 3E, one embodiment of the inventiondisclosed herein depicts an “off line” inorganic coating depositionapparatus that could be used to coat a substrate produced at a differentfacility. For example, in one embodiment the equipment design shown inFIG. 3E may be incorporated into a stand-alone process step at aconverter. In this embodiment, a packaging substrate 102 is unwound fromunwind roll 96, passed over a series of flame head assemblies 82 whichmay flame treat and/or deposit an ultra-thin coating(s) on to theexposed surface of the substrate 102, while concurrently the oppositeexposed surface of the substrate 102 is being cooled with spray coolantfrom coolant nozzles 130 to dissipate heat and control or preventdegradation or melting of the substrate 102. In this embodiment, chillrolls or other thermal applicators are not required to keep thesubstrate 102 from degrading or overheating due to the thermal inputsfrom exposure to the burners 82. The flame head assembly geometry,substrate line speed, coolant spray temperature and precursorconcentration could be configured in various contexts to produce thedesired thickness(es) of ultra-thin coating(s) to be deposited on theparticular packaging substrate. Industrial spray coolants that may beutilized in this embodiment may include aromatics, silicate-ester(COOLANOL 25R), Aliphatic (PAO), silicone (SYLTHERM XLT) or others asknown in the art. Typical processing conditions are as follows: linespeeds from 200 to 1500 ft/min (60 m/min to 450 m/min); chill rolltemperatures of 40 to 80° C.; the flame pretreatment with burner to filmdistance of 5 mm for flame pretreatment, a fuel to air ratio of 0.90 to0.95 for the flame treatment step, a natural gas flow rate of 100liters/min for a 1 meter wide line; the deposition step with burner tofilm distances of 5 to 45 mm, a fuel to air ratio 1.0, gas flow rates of70 to 105 liters/min for a 1 meter wide line, a precursor concentrationof 0.0001 mole % to 0.01 mole % of the gas stream. The plasmatemperatures have exhibited good results at 1200° C. with a rangecovering 650° C. to 1450° C. The above conditions will produce a coatingwith a WVTR of <0.2 g/m²/day and an OTR<20 cc/m²/day.

It should be noted that the embodiments shown in FIGS. 2A-3E and FIGS.5A-5I may utilize plasma-enhanced chemical vapor deposition (PECVD)apparatus and methods to accomplish the coating process as describedherein. As such, the depicted embodiments are not be construed as beinglimited to flame CCVD methods. Whenever the term “flame” or itsanalogues such as “flame head” or “flame head assembly” are used herein,it is interpreted as including “plasma” and its analogues, andequivalent laser ablation equipment. The plasma may be manipulated by anelectromagnetic field in proximity to the plasma source so as to directthe ions generated from the plasma reaction on to the substrate surfaceto be coated. Thus CCVD is not limiting to the product made, but is justone enabling method used to accomplish making of the described producton the film fabrication line. As previously described herein,alternative embodiments of the apparatus and systems disclosed in FIGS.2A-3E may be independently be configured to provide flame treatment ofthe substrate, to apply a primer coating and/or to apply barriercoatings at open atmosphere to the substrate as it moves along themanufacturing line.

FIG. 4 is a structural diagram depicting an embodiment of a coatedsubstrate 120. In the depicted embodiment, a film or paper substrate 122is primed with a pure or substantially pure silica layer 124. Thesubstrate 122 with silica layer 124 is then coated with additional oxidelayer 126 and a subsequent metal or oxide layer 128. Oxide layers 126,128 may be comprised of silica mixed with an additional chemicaladditive or “dopant” for purposes of enhancing the reactivity of theprimed surface 124 with additional desired coatings. In one embodiment,the metal barrier layer deposited by the apparatus and method describedherein has a thickness between 5 and 50 nm, with an optical density ofover 30%. The metal barrier layer may comprise aluminum, copper, iron,manganese, zinc and/or other metals as dictated by the needs of theuser. In other embodiments, layer 128 is an oxide layer deposited viaCCVD or layer 128 is a metal layer deposited by conventional vacuummetallization technology.

FIGS. 5A-5I depict various apparatus in which various embodiments of theinvention disclosed herein may be configured as desired by the user.FIG. 5A discloses a configuration wherein the chemical precursors 504are fed into the flame fuel line 502 prior to being mixed with air fromthe air line 506 and combusted at the flame head 508 as shown. FIG. 5Bdepicts a configuration wherein the chemical precursors 504 are fed intothe air line 506 prior to being mixed with fuel from the fuel line 502,which in this embodiment is natural gas, and combusted at the flame head508 as shown. FIG. 5C discloses a configuration were chemical precursors504 are fed into an air line 506 and a fuel line 502 prior to beingmixed at a fuel/air mixer 510 and combusted at the flame head 508 asshown. In this embodiment, different chemical precursors may be utilizedand fed into the air line and fuel line prior to mixing at the fuel/airmixer. FIG. 5D discloses wherein a chemical precursor is introducedafter the fuel and air constituents have mixed at the fuel/air mixer asshown. The resulting mixture is then combusted at the flame head asdescribed herein. FIG. 5E discloses a configuration wherein one or morechemical precursors may be mixed at the fuel/air mixer prior to theintroduction of an additional chemical precursor downstream and which isthereafter combusted at the flame head as shown. FIG. 5F discloses aconfiguration where the chemical precursor is introduced at the pointwhere the fuel and air are mixed. The resulting mixture is thencombusted at the flame head as described herein. FIG. 5G discloses aconfiguration wherein the chemical precursor is sprayed or otherwiseinjected into the existing flame produced by the flame head as shown.FIG. 5H discloses a configuration where in the chemical precursor iscombusted into the flame head burner as shown. FIG. 5I discloses aconfiguration wherein a laser ablation apparatus 512 is used to generatethe vapors and/or ion stream 514 which is directed to a substrate forcoating thereon. In the embodiments disclosed in FIGS. 5A-5I, it will beevident to one of ordinary skill in the art that various fuel, air andchemical precursor species may be utilized to generate the desiredcoatings upon the film substrate passing in the desired proximity of theflame head as described herein. The various embodiments shown in FIGS.5A-5I may be integrated into the various in-line and standalone filmsubstrate manufacturing and processing environments as disclosed herein.

To describe certain embodiments of the inventive apparatus and methodsdisclosed herein, the following examples are provided. Once havingunderstood the examples set forth herein, one of ordinary skill in theart should be able to apply the apparatus and methods disclosed hereinto other chemical deposition methods, and such applications are deemedto fall within the scope of the invention disclosed herein. Thefollowing examples are for illustrative purposes and are not to beconstrued as limiting the scope of the invention. In the examples, theprimer coating deposition was performed using CCVD in an open atmosphereenvironment. The chemical precursors consisted of TEOS in a methane airfeed through a film flame treater with a flame temps of 800° C. to 1200°C. unless otherwise indicated.

Example 1 SiO₂ Deposition on OPP Polymer by Roll Coater

As an example and for comparative purposes, a biaxially oriented OPPpolymer film substrate was flame treated first on the inside surface ofthe roll. Conditions for the flame treatment of film include: line speedof about 184 feet/min, a burner to film distance of about 5 mm, and afuel to air ratio of about 1.0. Following flame treatment step, the filmwas run through the roll coater a second time to deposit a silica layer.Conditions for the silica layer deposition include: line speed of about184 feet/min, a burner to film distance of about 5 mm, and a fuel to airratio of about 1.0, TEOS concentration of about 0.00379 mole percentagefor both of the flame treatment and silica deposition runs.

The deposition of silica is greatly enhanced by the flame treatment stepprior to the treatment with silica. This is demonstrated in FIG. 6 for asingle deposition pass of silica via information collected by XPS. Theamount of silica, as determined by signal strength, has a 70% increasein silica deposited. Signal without flame pretreatment is 290 counts persecond (CPS) at a peak maximum, while the max signal is 500 counts persecond for a single pass of silica after flame treatment. In otherwords, the silica content increased from 0.18 atomic % silicon withoutflame pretreatment to 0.23 atomic % silicon.

The pretreatment was so successful that multiple laps of silica weredeposited after a flame pretreatment was utilized. This is shown in FIG.7 for signal strength (CPS) vs. binding energy (eV) from XPS. The amountof silica increase during each pass, as can be clearly seen. In terms ofatomic % of silicon present, 1, 2, and 3 deposition passes of silicaresult in 0.23%, 0.26%, and 0.44%, respectively.

The ultimate arbiter of effectiveness is barrier of the deposited silicalayer. All of the samples from above in this example were metallizedunder standard vacuum metallization conditions to an optical density of2.3. The atomic percentage of silicon atoms on the film surface, WVTR,and OTR values are shown in FIG. 8 and plotted versus the number ofsilica deposition passes. All samples were flame treated before thesilica deposition passes except for the first sample labeled with ablack oval, which had no flame pretreatment before a single silicadeposition. Flame treatment and increasing number of silica passesresult in lower WVTR and OTR, or increasing barrier. This increasingbarrier results from a higher quality or more effective layer ofaluminum metal deposited on the silica primed film.

Example 2 High Speed Deposition on OPP Film

The current example is a biaxially oriented polypropylene (BOPP) placedon a roll to roll coater as disclosed herein for a single pass flametreatment and single layer silica coating deposited in one pass. Typicalprocessing conditions are as follows: line speed at about 900 ft/min(275 m/min); chill roll temperatures at about 54 degrees Celsius; theflame pretreatment with burner to film substrate distance of about 5 mmfor flame pretreatment, a fuel to air ratio of about 0.95 for the flamepretreatment step, a natural gas flow rate of about 100 liters/min for a1 meter wide line; the silica coating deposition step with burner tofilm distances of about 5 to 10 mm, a fuel air ratio of about 1.0, gasflow rates of about 75 to 100 liters/min for a 1 meter wide line, aprecursor concentration of in the range of about 0.0001 mole % to 0.01mole % of the gas stream and plasma temperatures at 1200 degreesCelsius. The film samples were then metallized under standard conditionsto an optical density of 2.5. The above described operating conditionsproduced a film substrate with a WVTR of <0.2 g/m²/day and an OTR of <20cc/m²/day. WVTR and OTR data for a variety of working distances (flameburner to film substrate distance), gas flow rate, and precursorconcentration (TEOS) are given in Table 1.

TABLE 1 Working Precursor Sample Distance, Conc, Gas Flow, WVTR, OTR,Number mm Mole % l/min g/m²/day cc/m²/day 1 5.00 0.0038 75.00 0.05 10.92 5.00 0.0038 100.00 0.12 12.8 3 10.00 0.0038 75.00 0.08 10.5 4 10.000.0038 100.00 0.08 6.86 5 5.00 0.0049 75.00 0.09 9.09 6 5.00 0.0049100.00 0.12 17.7 7 10.00 0.0049 75.00 0.15 10.5 8 10.00 0.0049 100.000.09 9.75 9 5.00 0.0095 75.00 0.07 11.8 10 5.00 0.0095 100.00 0.13 10.111 10.00 0.0095 75.00 0.09 10.1 12 10.00 0.0095 100.00 0.16 25.2

The data in Table 1 demonstrates the robustness of the silica depositionand primer process. The speeds employed in this example are similar, ifnot identical, to the line speeds in the typical film substrateproduction process.

Example 3 Multiple Layer Silica Deposition on OPP Film

Experiments were conducted with multiple laps over a film to producepure silica coating between 10 to 50 nm. The coatings were producedunder the following conditions: line speeds of about 600 to 900 FPM (180m/min to 275 m/min), the flame treatment with flame burner to filmsubstrate distance of about 5 mm for the flame treatment step, a fuel toair ratio of about 0.95, and a natural gas flow rate of about 100liters/min for a 0.3 meter wide line. For the coating deposition step, aflame burner to film substrate distance of about 5 to 15 mm, a fuel toair ratio of about 1.0, gas flow rates of about 75 to 100 liters/min fora 0.3 meter wide line, and a precursor concentration in the range of0.0001 mole % to 0.01 mole % of the gas stream. The plasma temperatureswere about 1250 degrees Celsius. A number of silica laps were madebetween about 36 and 72.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the specification and claims are to be understoodas being modified in all instances by the term “about.” Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present invention. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques. While the invention has been particularly shown anddescribed with reference to a preferred embodiment, it will beunderstood by those skilled in the art that various changes in form anddetail may be made therein without departing from the spirit and scopeof the invention.

We claim:
 1. A system for coating a packaging film substrate with aninorganic oxide layer comprising: at least one flame treatment flamehead assembly supplied with no inorganic oxide precursor; one or moredeposition flame heads supplied with at least one inorganic oxideprecursor placed in series on at least one deposition flame headassembly; wherein said substrate passes through said flame treatmentflame head assembly before said substrate passes through said depositionflame head assembly, and wherein said at least one flame treatment flamehead assembly and said one or more deposition flame heads are at openatmosphere.
 2. The system of claim 1 wherein said at least one flametreatment flame head assembly or said at least one deposition flame headassembly comprises multiple flame head assemblies oriented in parallelrows perpendicular to a substrate movement direction.
 3. The system ofclaim 1 wherein said at least one flame treatment flame head assembly orsaid at least one deposition flame head assembly comprises a square orrectangular shaped flame head assembly.
 4. The system of claim 1 whereinsaid at least one flame treatment flame head assembly or said at leastone deposition flame head assembly comprises multiple flame headsassemblies oriented in rows parallel to a substrate movement direction.5. The system of claim 1 wherein said at least one flame treatment flamehead assembly or said at least one deposition flame head assemblycomprises a curved flame head assembly.
 6. The system of claim 1 whereinsaid at least one flame treatment flame head assembly or said at leastone deposition flame head assembly is oriented at an angle relative to asurface of said substrate.
 7. The system of claim 1 wherein saidsubstrate passes through said flame head assemblies as it passes over aportion of said at least one chill roll.
 8. The system of claim 1wherein said inorganic precursors are fed into a flame fuel line of saiddeposition flame heads prior to being mixed with air from an air lineand combusted at said flame heads.
 9. The system of claim 1 wherein saidinorganic precursors are fed into an air line of said deposition flameheads prior to being mixed with fuel from a fuel line and combusted atsaid flame heads.
 10. The system of claim 1 wherein said inorganicprecursors are fed into an air line and a fuel line of said depositionflame heads prior to being mixed and combusted at said flame heads. 11.The system of claim 1 wherein said inorganic precursors are mixed withan air/fuel mixture prior to being fed to said deposition flame heads.12. The system of claim 1 wherein said inorganic precursors is injectedinto a flame produced by said deposition flame heads.
 13. The system ofclaim 1 further comprising an air knife flame redirect.